of milwaukee



Patented Nov. 9, 1926.

UhllTEi) STATES PATENT @FFIQE.

JOSEPH B. OESCI-I; OF MILWAUKEE, WISCONSIN, ASSIGNOR TO THE NEWPORT GOM-PANY, OF MILWAUKEE, WISCONSIN, .A CORPORATION OF DELAWARE.

TETRAKISAZO DYE AND TI-IE PROCESS OF MANUFACTURE.

No Drawing.

This invention relates to tetrakisazo dyes capable of dyeing unmordantedcotton orange to brown shades of great fastness to light. The new dyesare derived from aminoazo Application filed September 19, 1925. SerialNo. 57,316.

ponents, and one molecular proportion of an end component consisting ofsalicylic acid and its substitution products.

These new dyes correspond to the generall bodies of the benzene series,two molecular formula: n proportlons of In-tolu1d1ne as middle com- 'NN--NN V CH3 coon --N=N -N=N H I I I (SOQH) 1 or 2 (Halogen) 0 or 1(CH3)00I2 (CH )00z-l The process of manufacture consists in combining anaminoazo dye of the benzene .series with m-toluidine, diazotizing theintermediate disazo dye thus obtained, combining the same withm-toluidine, diazotizing the resulting trisazo dye, and combining thelatter with salicylic acid or a substitution product thereof.

Without limiting our invention to any particular procedure, thefollowing example, in which parts by weight are expressed, is given toillustrate the application of our invention in the preferred form:

Dissolve 418 parts of aminoazotoluol disulfonio acid sodium salt in 300parts of water and diazotize at 0-5 C. by adding 6.9 parts of sodiumnitrite. This solution is then added to 40 parts of hydrochloric acidB.). Stir and correct excess nitrate. To the diazo compound add asolution of 11.2 parts m-toluidine dissolved in 150 partsof water and 11 parts of hydrochloric acid (20 B.). Stir and add slowly asolution of31 parts of sodium acetate, stirring until coupling is completed. Add 20parts of sodium carbonate (in solution) and 7.3 parts of sodium nitriteRun themiXture into a so- 65 The dye thus obtained is in the shape oflution 81 parts of hydrochloric acid (20 Be.) in 150 parts of water.Stir, correct excess nitrite, and add a solution of 11.2 parts ofm-toluidine in 13.9 parts'of hydrochloric acid (20 Be.) and 150 parts ofwater. Stir and add slowly 16.5 parts of sodium acetate (in solution).Gontinue stirring until coupling is completed. Now add 88 parts ofsodium carbonate and stir until complete solution is obtained. Then add191 parts of hydrochloric acid (20 B.) and filter. Dilute the filtercake with about 1000 parts of water and add 4 parts of sodium hydroxide.Stir until complete solution is obtained; then add 7 parts of sodiumnitrite and run the mixture into a solution of 35 parts of hydrochloricacid (20 Be.) in 400 parts of water. Stir, correct excess nitrite, andadd the diazo component to a solution of 13.8 parts of salicylic acidwhich has been previously dissolved in 81.8 parts of sodium carbonateand 200 parts of water. Stir and salt out, filter and dry.

The structuralv formula of the specific dye formed in the above exampleis best represented by the following:

its sodium salt a dark powder, soluble in Water to a brown solutionwhich changes into a reddish brown by the addition of caustic soda. Withhydrochloric acid the dye separates as a greenish-brown precipitate. Thepowder is insoluble in organic solvents such as absolute alcohol, ether,or benp-sulfonic sodium salt p-phenylencdiamine 11am aware. thatnumerous details ofthe processinay be'var ed through a wide range.

without departing from the spirit of this invention, and V I do not,desire limiting the patent granted other than as necessitated by theprior art.

O V i O OCHL --N=N l l (SO Hll on 2 groups (CH 0 01:2 groups this dye,being in the shape of its sodium salt a dark powder, soluble in waterto a brown solution, changing to a reddish-brown with sodium hydroxide;with hydrochloric acid separating-outaaabrown precipitate; said powderbeing insoluble in organic solvents such as absolute alcohol, ether, orbenzene,

SO Na 3. The method of preparing a tetrakisazo CH3 SOsNa CH zene and isdestroyed by strong reducing agents. It dyes cotton a yellowish brown.

The products of reduction of the specific dye formed in the aboveexample are probably the following NH: OH

NH NH: 2 molecules of methyl-p, p-amino-salicylic acid phenylenediamincI :claim as my invention:

'1. As a new article of manufacture a tetralrisazo dye as hereindescribed, haying most 2:) probably, the following formula CH CO OH(Halogen) 0 or 1 groups (CH3) 0 or 1 groups and being destroyed bystrong reducing agents; the dyeings on cotton being orange to brown.

2. As a new article of: manufacture a tetrakisazodye haying mostprobably the general formula:

dye of the general formula:

coon

(Halogen) 0 or 1 groups (CH3) 0 or 1 groups I 5. Materials dyed with thedye prepared according to claim 2.

lntestimony whereof I have hereunto subscribed my name.

JOSEPH B. OESCH.

